EP1585712B1 - Procede de preparation d'oligomeres butene et de tert-butylethers a partir de flux c4 contenant de l'isobutene - Google Patents

Procede de preparation d'oligomeres butene et de tert-butylethers a partir de flux c4 contenant de l'isobutene Download PDF

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EP1585712B1
EP1585712B1 EP03799530.5A EP03799530A EP1585712B1 EP 1585712 B1 EP1585712 B1 EP 1585712B1 EP 03799530 A EP03799530 A EP 03799530A EP 1585712 B1 EP1585712 B1 EP 1585712B1
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Prior art keywords
isobutene
butene
stage
oligomerization
carried out
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EP1585712A1 (fr
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Udo Peters
Dieter Reusch
Andreas Beckmann
Dirk Röttger
Jochen Praefke
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Evonik Operations GmbH
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Evonik Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
    • C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/58—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/14875—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds
    • C07C7/14891—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds alcohols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention relates to a process for the preparation of butene oligomers and tert-butyl ethers from C 4 -hydrocarbon streams, by reacting the isobutene to butene oligomers, in particular isobutene oligomers and tert-butyl ethers and their removal from the C 4 streams.
  • Isobutene, linear butenes and their derivatives are obtained in large quantities from technical C 4 cuts, for example the C 4 cut from steam crackers or FCC units. These mixtures consist essentially of butadiene, the monoolefins isobutene, 1-butene and the two 2-butenes and the saturated hydrocarbons isobutane and n-butane. Because of the low boiling point differences of the ingredients and their low separation factors, a distillative work-up is difficult and not economical. The recovery of linear butenes and other products is therefore usually through a combination of chemical reactions and physical separation operations.
  • the C 4 cuts are worked up differently.
  • the first step common to all refining variants, is the removal of most of the butadiene.
  • Butadiene can be well marketed or own consumption, it is separated by extraction or extractive distillation. Otherwise, it is selectively hydrogenated to linear butenes to a residual concentration of about 2000 ppm by mass.
  • a hydrocarbon mixture remains (so-called raffinate I or hydrogenated crack C 4 ), which contains the olefins isobutene, 1-butene and 2-butenes (cis and trans) in addition to the saturated hydrocarbons n-butane and isobutane.
  • C 4 streams which typically contain not more than 1% butadiene (C 4 stream of FCC (fluid catalytic cracker), raffinate I or hydrogenated crack C 4 ) are hydrogenated and hydroisomerized, that is, it is selectively hydrogenated butadiene present to a residual content of less than 5 ppm and simultaneously isomerizes 1-butene to 2-butenes.
  • FCC fluid catalytic cracker
  • raffinate I or hydrogenated crack C 4 are hydrogenated and hydroisomerized, that is, it is selectively hydrogenated butadiene present to a residual content of less than 5 ppm and simultaneously isomerizes 1-butene to 2-butenes.
  • 1-butene is one of the target products, the following procedure can be followed: from raffinate I or hydrogenated crack C 4 isobutene is removed by chemical reaction. After removal of the isobutene remains a hydrocarbon mixture (raffinate II) containing the linear butenes and the saturated hydrocarbons isobutane and n-butane. This mixture can be further fractionated by distillation, for example in isobutane and 1-butene and a mixture of the two 2-butenes and n-butane. From the 1-butene-containing fraction 1-butene can be obtained in high purity in further distillation steps, which contains only small amounts of isobutane.
  • the chemical reaction of the isobutene can be carried out with water to tert-butyl alcohol (TBA).
  • TSA tert-butyl alcohol
  • Another possibility is to oligomerize the isobutene and separate the oligomerizate.
  • the disadvantage here is that in the complete removal of isobutene by oligomerization, a large part of the present linear butenes is converted into co- or homo-oligomers.
  • Another disadvantage is the partial isomerization of 1-butene to the 2-butenes.
  • isobutene Another possibility for the separation of isobutene is its reaction with alcohols, for example methanol or ethanol, to give the corresponding tertiary butyl ethers.
  • alcohols for example methanol or ethanol
  • tertiary butyl ethers especially MTBE, as octane enhancers in gasoline fuels is increasingly critical because of groundwater contamination in the US. It can not be ruled out that the current and future discussions lead to the restriction of the use of tertiary butyl ethers in fuels.
  • EP 0 048 893 discloses a process for the simultaneous production of isobutene oligomers and alkyl tertiary butyl ether from C 4 cuts in a reactor.
  • the catalyst used is an acidic ion exchange resin, which is partially occupied by metals of the seventh and eighth subgroups of the Periodic Table of the Elements in elemental form (oxidation state 0).
  • the products and the unreacted C 4 hydrocarbons are separated by distillation.
  • about 8% of the linear butenes are lost by oligomerization.
  • the loss of 1-butene is 7%.
  • the main drawback of this process is that no complete isobutene conversion is achieved, so that the isobutene content in the separated C 4 -hydrocarbon fraction is too high to obtain a specification-compliant 1-butene.
  • US 5,723,687 also describes a process for the simultaneous production of isobutene oligomers and MTBE or ETBE by reacting a C 4 cut , for example raffinate I, in the presence of methanol or ethanol over an acidic ion exchange resin in a reactor.
  • a C 4 cut for example raffinate I
  • methanol or ethanol over an acidic ion exchange resin in a reactor.
  • a disadvantage of this process is the low isobutene conversion, which according to the examples is only between 78 and 94%
  • EP-A-1199296 teaches the removal of isobutene from C 4 streams by acidification of the isobutene with an alcohol to produce tert-butyl ethers in at least two reaction stages, the last reaction stage being carried out as a reactive distillation. It can thereby obtain a high purity 1-butene from the liberated from isobutene mixture.
  • WO-A-02064531 discloses a process for producing high purity diisobutene by oligomerizing isobutene-containing hydrocarbon mixtures on a solid acidic ion exchange resin, wherein the acidic ion exchange resin comprises sulfonic acid groups whose protons are exchanged for 50 to 80% with metal ions.
  • EP-A-1074534 describes the carrying out of an oligomerization of isobutene in the presence of MTBE or methanol, the molar ratio of the MTBE or of the methanol to isobutene being more than 0.1.
  • EP-A-0081041 discloses the catalytic hydrogenation of polyunsaturated hydrocarbons in a C 4 stream in the presence of carbon monoxide in a concentration of 0.05 to 20 wppm.
  • the isobutene can be completely removed from a largely butadiene-free C 4 -hydrocarbon stream with only slight losses of linear butenes by reacting a portion of the isobutene in a first reaction step on acidic catalysts, their activity by adding moderators or Ion exchange has been modified, is oligomerized and that in a second reaction step, the remaining isobutene is removed by reaction with alcohol to a tert-butyl ether in a reactive distillation column.
  • the invention accordingly provides a method according to claim 1.
  • Butene oligomers in the context of the present invention are in particular isobutene oligomers such as di-, tri- or tetramers of isobutene. To a lesser extent, these may also contain cooligomers with or from 1- or 2-butenes.
  • isobutene-free residual streams which are suitable for the preparation of 1-butene can be produced from C 4 streams.
  • the isobutene-free residual streams contain, in addition to the unreacted constituents of the C 4 feed (usually C 4 -aliphatic), only n-butenes, ie 1-butene, cis-2-butene and trans-2-butene.
  • 1-butene can be separated off by distillation (the i-butane separated off together with the 1-butene, if appropriate, can be separated from 1-butene in a second distillation step).
  • the remaining 2-butenes which may still contain 1-butene, are in turn, wished feedstocks for the preparation of linear butene oligomers where the presence of isobutene would lead to undesirably high levels of branching.
  • Suitable isobutene-containing C 4 streams are, for example, light petroleum fractions from refineries, C 4 fractions from crackers (for example steam crackers, hydrocrackers, crackers), mixtures of Fischer-Tropsch syntheses, mixtures from the dehydrogenation of butanes, mixtures from skeletal isomerization of linear butenes and Mixtures formed by metathesis of olefins.
  • C 4 fractions from crackers for example steam crackers, hydrocrackers, crackers
  • Fischer-Tropsch syntheses mixtures from the dehydrogenation of butanes
  • mixtures from skeletal isomerization of linear butenes and Mixtures formed by metathesis of olefins are described in the specialist literature, K.Weissermel, HJ Arpe, Industrial Organic Chemistry, Wiley-VCH, 5th Edition, 1998, pages 23-24; 65-99; 122-124 .
  • C 4 fractions from steam crackers which are operated primarily for the production of ethene and propene and in which, for example, refinery gases, naphtha, gas oil, LPG (liquefied petroleum gas) and NGL (natural gas liquid) or cat crackers are used as raw materials.
  • the by-produced C 4 cuts contain different amounts of isobutene depending on the cracking process.
  • Other main constituents are 1,3-butadiene, 1-butene, c-2-butene, t-2-butene, n-butane and i-butane.
  • Typical isobutene contents in the C 4 fraction are from 18 to 35% for C 4 fractions from steam crackers and 10 to 20% for FCC crackers.
  • polyunsaturated hydrocarbons such as 1,3-butadiene
  • This can be done by known methods, for example by extraction, extractive distillation or complex formation (cf. K.Weissermel, HJ Arpe, Industrial Organic Chemistry, Wiley-VCH, 5th Edition, 1998, pages 119-121 ).
  • 1,3-butadiene can be selectively hydrogenated to linear butenes, such as. B. described in EP 0 523 482 .
  • 1,3-butadiene can be selectively hydrogenated to linear butenes, such as. B. described in EP 0 523 482 .
  • the 1,3-butadiene can be at least partially removed.
  • the polyunsaturated hydrocarbons present in the isobutene-containing C 4 streams are preferably catalytically hydrogenated prior to the oligomerization in stage a).
  • the polyunsaturated hydrocarbons are mainly 1,3-butadiene; 1,2-butadiene, butenine and 1-butyne are contained in a much smaller amount.
  • the hydrogenation can take place in a single-stage or multistage hydrogenation process in the liquid phase on a palladium contact. In order to lower the content of 1,3-butadiene below 1000 ppm, in the last stage of the hydrogenation, addition of a moderator is used, which increases the selectivity of the palladium contact.
  • the moderator used is preferably carbon monoxide, which is added in a proportion of 0.05 to 100 ppm by weight.
  • the content of polyunsaturated hydrocarbons in the feed to this stage should be less than 1%, preferably less than 0.5%.
  • SHP selective hydrogenation process
  • amounts of greater than 1% of polyunsaturated hydrocarbons, such as 1,3-butadiene, are contained in the isobutene-containing C 4 streams, they are reacted in upstream hydrogenations. These hydrogenations are preferably carried out in the liquid phase on a palladium contact. Depending on the content of unsaturated hydrocarbons, the hydrogenation can be carried out in several stages. For the conversion of crack C 4 from a steam cracker with a content of 1,3-butadiene of typically 38-45%, a two-stage version of the hydrogenation has been proven. In this case, individual or all stages may be equipped with a partial product return. In the discharge, concentrations of 1,3-butadiene less than 1% are available, so that a further reaction can take place in an SHP stage.
  • polyunsaturated hydrocarbons such as 1,3-butadiene
  • the hydrocarbon mixtures with isobutene and linear butenes used in the process according to the invention preferably have the following compositions: Table 1 Typical compositions of hydrocarbon mixtures used in the process of the invention. steam cracker steam cracker catcracker component HCC 4 HCC 4 / SHP Raff. I Raff.
  • HCC 4 / SHP composition HCC 4 in which residues of 1,3-butadiene in an SHP were further reduced.
  • Raff. I raffinate I
  • - Raff. I / SHP Composition Raff. I, in which residues of 1,3-butadiene in an SHP were further reduced.
  • CC 4 typical composition of cracking C 4 obtained from a cracker.
  • - CC 4 / SHP Composition CC 4 , in which residues of 1,3-butadiene in a SHP were further reduced.
  • the raffinate I or HCC 4 is, among others, a preferred used isobutene-containing hydrocarbon mixture in the context of this invention. Since plants for the workup of C 4 hydrocarbons are usually built up as a strand (combination of several plants), it is possible, however, for the raffinate I or HCC 4 to pass through one or more other process stages before it enters the process according to the invention. In this way, an individually adapted overall concept for processing with the corresponding product portfolio can be realized in each case.
  • Typical process stages which may be upstream of the process according to the invention, are water washing, adsorbent purification, selective hydrogenation, TBA synthesis, drying and distillation.
  • hydrophilic components of the hydrocarbon mixture containing isobutene and linear butenes can be completely or partially removed, for example nitrogen components.
  • nitrogen components are acetonitrile or N-methylpyrrolidone (which may be obtained, for example, from a 1,3-butadiene extractive distillation).
  • Oxygen compounds eg acetone from FCC crackers
  • the isobutene-containing hydrocarbon stream is saturated after a water wash with water. In order to avoid a two-phase in the subsequent process steps in the reactor, the reaction temperature should be about 10 ° C above the temperature of the water wash there.
  • Adsorbers are used to remove impurities. This can be advantageous, for example, if noble metal catalysts are used in one of the process steps. Often, nitrogen or sulfur compounds are removed via upstream adsorbers. Examples of adsorbers are aluminum oxides, molecular sieves, zeolites, activated carbon, metal-impregnated clays. Adsorbers are sold by various companies, for example, the company Alcoa (Selexsorb ® ).
  • Polyunsaturated compounds, in particular 1,3-butadiene, which are still present in small amounts, are obtained by further selective hydrogenation (cf. EP 0 081 041 ; Petroleum, coal, natural gas, petrochem. 1986, 39, 73).
  • the SHP can be operated both as part of a butadiene hydrogenation (see above), or as an independent process step.
  • TBA tert-butanol
  • water contained in the isobutene-containing hydrocarbon mixture which may originate, for example, from water scrubbing or TBA synthesis, can be removed by known drying processes. Suitable methods are, for example, the distillative separation of the water as an azeotrope. In this case, an azeotrope containing C 4 hydrocarbons can often be utilized or entrainers are added.
  • the drying of the hydrocarbon mixture can be advantageous for a variety of reasons, such as reducing the formation of alcohols (mainly tert-butyl alcohol) in the oligomerization / etherification, preventing (uncontrolled) water moderation in the butene oligomerization, avoiding technical problems by precipitation of water or ice low temperatures (eg intermediate storage).
  • alcohols mainly tert-butyl alcohol
  • Distillation steps can for example be used to remove impurities in order to obtain fractions (for example, low boilers such as C3 hydrocarbons, high boilers such as C 5 hydrocarbons) or with different isobutene.
  • fractions for example, low boilers such as C3 hydrocarbons, high boilers such as C 5 hydrocarbons
  • isobutene This can be done either directly with the raffinate I or the HCC 4 or after one or more other process stages have been run through.
  • direct distillation of the raffinate I or the HCC 4 s for example, a separation in a 2-butenes and n-butane impoverished, isobutene richer fraction possible.
  • the partial oligomerization in stage a) of the isobutene can in principle be homogeneous, d. H. using reaction-soluble catalysts, or heterogeneous, i. be carried out using catalysts insoluble in the reaction mixture.
  • the disadvantage of the homogeneous process is that the catalyst leaves the reactor with the reaction products and unreacted educts, from which it has to be separated off, worked up and disposed of or recycled.
  • the partial oligomerization of the isobutene preferably carried out on solid heterogeneous catalysts, which are often also arranged in a fixed bed, so that a complex catalyst removal is omitted.
  • Suitable ion exchange resins are, for example, those prepared by sulfonation of phenol / aldehyde condensates or cooligomers of vinyl aromatic compounds.
  • aromatic vinyl compounds for preparing the cooligomers are: styrene, vinyltoluene, vinylnaphthalene, vinylethylbenzene, methylstyrene, vinylchlorobenzene, vinylxylene and divinylbenzene.
  • the co-oligomers formed by reacting styrene with divinylbenzene are used as precursors for the preparation of sulfonic acid ion exchange resins.
  • the properties of these resins can be varied by the manufacturing process.
  • the resins can be prepared gel-like, macroporous or spongy. Strongly acidic resins of the styrene-divinylbenzene type become u. a. sold under the following trade names: CT 151 from Purolite, Amberlyst 15, Amberlyst 35, Amberlite IR-120, Amberlite 200 from Rohm & Haas, Dowex M-31 from DOW, K 2611, K 2431 from Bayer.
  • the ion exchange capacity of the completely H + -form resins is typically between 1 and 2, especially 1.5 to 1.9, moles of H + per liter of wet resin (commercial grade).
  • macroporous resins such as, for example, K 2431 from Bayer, Amberlyst 15 or Amberlyst 35 from Rohm & Haas.
  • the pore volume is preferably 30 to 60 ml / g, in particular 40 to 50 ml / g (based on commercially available water-moist resin).
  • the grain size of the resin is preferably between 500 .mu.m and 1500 .mu.m, in particular between 600 .mu.m and 1000 .mu.m.
  • the particle size distribution can be narrowed or further selected.
  • ion exchange resins having a very uniform grain size can be used.
  • the ion exchange resins can be used as moldings, such as cylinders, rings or spheres.
  • the acidic ion exchange resin is expediently adjusted to an activity which allows the oligomerization of the isobutene, but hardly catalyzes the co-oligomerization of isobutene with linear butenes, the oligomerization of the linear butenes and the isomerization of the linear butenes. Furthermore, the heat development in the reactor becomes technically good controllable value.
  • the setting of the desired catalyst activity can be done with the help of moderators. These substances are passed over the catalyst together with the educt.
  • moderators for example, water, alcohols such as tert-butyl alcohol (TBA), methanol, isononanol or ethanol or ethers such as tert-butyl methyl ether (MTBE) can each be used as pure substance or mixtures.
  • TAA tert-butyl alcohol
  • methanol isononanol or ethanol
  • ethers such as tert-butyl methyl ether (MTBE)
  • MTBE tert-butyl methyl ether
  • the oligomerization in stage a) is therefore preferably carried out in the presence of these moderators.
  • molar ratios of 0.01 to 5, preferably 0.01 to 1, in particular 0.01 to 0.7 mol moderator per mole of isobutene have proven.
  • solid sulfonated ion exchange resins which have the desired activity without the addition of moderators are also used for the oligomerization.
  • These are in particular partially neutralized ion exchange resins in which 1 to 60%, preferably 1 to 30%, very particularly preferably 5 to 15% of the acidic protons of the sulfonic acid groups have been exchanged for metal ions.
  • metal ions replacing the protons alkali metal, alkaline earth metal, transition metal ions (groups 1 - 12 metal ions such as chromium, manganese, iron, cobalt, nickel, zinc ions) and aluminum ions and ions of the lanthanide group (rare earths) be used.
  • Preference is given to using alkali metal ions, in particular sodium ions. It is also possible that the ion exchange resin is loaded with two or more different metal ions.
  • the ion exchange resin For the preparation of the partially neutralized ion exchange resins, various methods, all of which are described in the specialist literature, can be used.
  • the ion exchange resin When the ion exchange resin is in the H + form, protons can be exchanged for metal ions. If the resin is present as a metal salt, metal ions can be replaced by protons with the help of acids. In principle, this ion exchange can take place both in organic and in aqueous suspension.
  • the ion exchange resin in the H + form is slurried with so much liquid that a well stirrable suspension is formed.
  • a solution containing the desired ions is added.
  • the partially exchanged ion exchange resin is washed and dried.
  • the amount of solvent for slurrying the ion exchange resin is typically one to ten times the intrinsic volume of the ion exchange resin.
  • the ion exchange is preferably carried out in the temperature range from 10 to 100 ° C, more preferably at 20 to 40 ° C.
  • the exchange is usually completed after 24 hours at the latest.
  • the catalyst is separated from the solution, e.g. By decantation or filtration, and optionally subsequently washed with a solvent. It is convenient to use the same solvent in which the catalyst was suspended.
  • drying can be carried out in vacuo or in an inert gas stream, for example in a stream of nitrogen.
  • the drying temperatures are typically between 10 and 120 ° C.
  • a preferred way of preparing the catalysts used in the process according to the invention is the exchange of protons for metal ions in the aqueous phase, washing the partially exchanged ion exchange resin with water and subsequent drying
  • the ions with which the resin is to be loaded may be present as solutions of hydroxides, or salts of organic or inorganic acids.
  • salts of polybasic acids and acid salts can be used. It is also possible to use compounds with other organic radicals, such as, for example, alkoxides or acetylacetonates.
  • the source of the metal ions is preferably metal hydroxides and salts of inorganic acids.
  • alkali metal hydroxides for example sodium hydroxide
  • alkali metal halides for example sodium chloride
  • alkali metal sulfates for example sodium sulfate
  • alkali metal nitrates for example sodium nitrate
  • alkaline earth metal hydroxides and alkaline earth metal nitrates can be prepared by the procedure described above.
  • a reactor in the process of the invention may contain a mixture of ion exchange resins of different reactivity. It is also possible that a reactor contains catalysts with different activity, arranged in layers. If more than one reactor is used, the individual reactors may be filled with catalysts of equal or different activity.
  • the reaction can be carried out in batches or preferably in continuous reactors, which are usually used in solid / liquid contact reactions.
  • continuous flow reactors is usually, but not exclusively, a fixed bed.
  • a concept other than fixed bed reactors are, for example, reactors in which the ion exchanger is suspended in a liquid phase (cf. Bayer Process ", petroleum and coal, natural gas, petrochemical, 1974, 27, No. 5, page 240 ).
  • the liquid may flow up or down. Usually, downflow of the liquid is preferred.
  • a cooling liquid flowing around the reactor may optionally have the same or opposite flow direction. Furthermore, it is possible to operate the reactor with product recirculation or in straight pass.
  • the ratio of length to diameter of the catalyst bed can be varied, either by the geometric dimensions of the reactor or by its degree of filling. With the same amount of contact and load (LHSV) thus different Leerrohr yorken can be achieved.
  • the reactors used in the technical process can be operated adiabatically, polytropically or practically isothermally.
  • Practically isothermal means that the temperature at any point in the reactor is at most 10 ° C higher than the temperature at the reactor inlet.
  • adiabatic operation of the reactors it is usually useful to connect several reactors in series and to cool between the reactors.
  • Reactors which are suitable for a polytropic or practically isothermal operation are, for example, tube bundle reactors, Stirred tank and loop reactors.
  • the temperatures at which the oligomerization is operated are between 5 and 160 ° C, preferably between 40 and 110 ° C.
  • the reaction can be carried out with and without the addition of an additional solvent.
  • the solvents used are preferably saturated hydrocarbons, in particular C 4 -, C 8 - or C 12 hydrocarbons. Very particular preference is the use of isooctane. When solvents are added, their proportion is 0 to 60% by weight, preferably 0 to 30% by weight.
  • the reaction of the invention can be carried out at a pressure equal to or above the vapor pressure of the feed hydrocarbon mixture at the respective reaction temperature, preferably at a pressure below 40 bar, d. H. the isobutene-containing hydrocarbon mixtures are present during the oligomerization wholly or partly in the liquid phase. If the reaction is to be carried out completely in the liquid phase, the pressure should be 2 to 4 bar higher than the vapor pressure of the reaction mixture in order to avoid evaporation problems in the reactors.
  • the total conversion of isobutene to oligomers can be adjusted by the type and amount of catalyst used, the reaction conditions set and the number of reactors. In the process according to the invention, 50 to 95% of the isobutene present in the starting material, in particular 60 to 90%, are oligomerized.
  • the reaction mixture of the partial isobutene oligomerization can be worked up differently.
  • the mixture is either passed directly into the etherification or before etherification, the butene oligomers are separated.
  • the separation of the oligomers and optionally of hydrocarbons having 5 to 7 carbon atoms is advantageously carried out by distillation.
  • the separated oligomer fraction contains mainly C 8 hydrocarbons. In addition to the diisobutene, this can also contain codimers and higher oligomers (C 12 , C 16 ,). This fraction can be separated in further distillation steps. For example, it is possible to separate a fraction with high-purity diisobutene in order to use them separately, for example for chemical syntheses. For use as a fuel component for gasoline engines, it may be necessary to separate high boiling components (preferably boiling point> 220 ° C).
  • butene oligomers in particular the C 8 olefins.
  • Methods for hydrogenating the products of the oligomerization to the corresponding paraffins are well known to those skilled in the art. Common methods for the hydrogenation of olefins are described, for example, in US Pat F. Asinger, "Chemistry and Technology of Monoolefins", Akademie Verlag, Berlin, 1957, pages 626-628 or DE 197 19 833 ,
  • the hydrogenation is carried out in the liquid phase over a solid catalyst which is not soluble in the hydrogenation product.
  • the hydrogenation catalysts used are preferably supported catalysts which consist of an inorganic carrier and contain as active metal platinum and / or palladium and / or nickel.
  • the temperature at which the hydrogenation is carried out is preferably in the range of 10 to 250 ° C and the pressure between 1 and 100 bar.
  • fractions After the hydrogenation, further fractions can be obtained by distillative separation. From these and from the unhydrogenated fractions, fuel additives of particular properties are obtainable by blending. Furthermore, some fractions can be used as solvents.
  • the isobutene-depleted C 4 -hydrocarbon mixture is reacted in the process according to the invention in a second reaction step (step b), in which the remaining isobutene is removed by addition of alcohol to the corresponding tertiary ether.
  • This C 4 -hydrocarbon mixture can, if required, additionally be isobutene-deficient C 4 Hydrocarbons (for example, Raffinate II, optionally purchased) are added.
  • These streams can come from other processes, for example a TBA synthesis or an isobutene separation via hydroisomerization / distillation (cf. EP 1 184 361 ).
  • the etherification of the isobutene is carried out as an acid-catalyzed reaction.
  • alcohols for primary, secondary, monohydric or polyhydric alcohols having 1 to 5 carbon atoms preferably methanol or ethanol are used.
  • the addition of the alcohol to the isobutene is carried out in the presence of an acid catalyst in at least two reaction stages, wherein the last reaction stage is carried out as a reactive distillation.
  • a reaction mixture is initially prepared on an acidic catalyst from the isobutene-poor C 4 stream and alcohol which, in terms of its isobutene, alcohol and tert-butyl ether concentration, is close to the thermodynamic equilibrium. For example, this is generally between 94 and 96% isobutene conversion for methanol / MTBE. This mixture is fed to the reactive distillation column, where a further portion of the isobutene is converted to the ether.
  • the one or more pre-reactors in which the alcohol is reacted with the isobutene to close to the thermodynamic equilibrium may be conventional fixed bed reactors (tube reactors, circulation reactors). They can be operated with or without partial recirculation, where appropriate the recycle stream is cooled.
  • the reactors are in the usual manner at 30 to 110 ° C and 5 to 50 bar abs . (bara) operated. Since the thermodynamic equilibrium between alcohol / isobutene and ether at low temperature is predominantly on the side of the ether, it is preferred, when using a plurality of pre-reactors, the first of the reactors at a higher temperature (high reaction rate) to operate as the following (utilization of equilibrium position).
  • the catalyst is either integrated in the packing, for example KataMax® ® ( EP 0 428 265 () Katapak ® EP 0 396 650 ) or MultiPak ® (utility model no. 298 07 007.3 ) or polymerized on moldings ( US 5,244,929 ).
  • the activity of the catalysts is that under the reaction conditions, the addition of alcohol to isobutene, but hardly the addition of linear butenes. Furthermore, they are unlikely to catalyze the oligomerization of linear butenes and dialkyl ether formation from two molecules of alcohol used. In view of a high yield of 1-butene, the activity for equilibration between the linear butenes should be low.
  • solid catalysts for example, zeolites, acid-activated Betonite and / or clays, sulfonated zirconium oxides, monomorillonites or acidic ion exchange resins can be used.
  • a preferred group of acidic catalysts in the process according to the invention are solid ion exchange resins with sulfonic acid groups.
  • Suitable ion exchange resins are, for example, those prepared by sulfonation of phenol / aldehyde condensates or cooligomers of vinyl aromatic compounds.
  • aromatic vinyl compounds for preparing the cooligomers are: styrene, vinyltoluene, vinylnaphthalene, vinylethylbenzene, methylstyrene, vinylchlorobenzene, vinylxylene and divinylbenzene.
  • the co-oligomers formed by reacting styrene with divinylbenzene are used as precursors for the preparation of ion exchange resins having sulfonic acid groups.
  • the resins can be prepared gel-like, macroporous or spongy.
  • Strongly acidic resins of styrene-divinylbenzene type are sold, inter alia, under the following trade names: Duolite C20, Duolite C26, Amberlyst A15, Amberlyst A35, Amberlite IR-120, Amberlite 200, Dowex 50, Lewatit SPC 118, Lewatit SPC 108, K2611, K2621, OC 1501.
  • the ion exchange resins can be used in their H form.
  • macroporous resins are used, such as Lewatit SCP 118, Lewatit SCP 108, Amberlyst A15 or Amberlyst A35, K2621.
  • the pore volume is 0.3 to 0.9 ml / g, in particular 0.5 to 0.9 ml / g.
  • the grain size of the resin is between 0.3 mm and 1.5 mm, in particular between 0.5 mm and 1.0 mm.
  • the particle size distribution can be narrowed or further selected.
  • ion exchange resins having a very uniform grain size can be used.
  • the capacity of the ion exchanger, based on the delivery form is 0.7-2.0 mol / l, in particular 1.1-2.0 mol / l.
  • the residual isobutene is removed by reaction with methanol to give MTBE.
  • the procedure is in particular such as in DE 101 02 082 described.
  • the isobutene poor C 4 -hydrocarbon mixture is fed together with methanol in the prereactor. There, a mixture is formed in which isobutene, methanol and MTBE are in equilibrium or nearly in equilibrium. This reaction mixture is introduced into the reactive distillation column.
  • methanol excess should be limited so that on the one hand a sufficient amount of methanol for the forming azeotrope of methanol and C 4 hydrocarbons on the other hand, not so much that methanol would enter the bottom product, so that a specification-compliant MTBE (methanol content preferably below 5000 wppm) is obtained. However, this only applies if the oligomers were previously separated. Otherwise, a mixture of MTBE and oligomers is obtained.
  • methanol content in the column feed is below the maximum allowable level, additional methanol may be added.
  • a methanol feed can be made at the top of the reactive distillation column via a separate device.
  • the zone above the catalyst packing consists of 5 to 20, in particular 10 to 15, separation stages.
  • the catalyst zone can be estimated with a distillative effect of 1 to 5 theoretical plates per meter packing height.
  • the separation zone below the catalyst comprises 12 to 36, in particular 20 to 30, separation stages.
  • the temperature of the column feed regardless of its composition, reaction pressure in the column and throughput between 50 ° C and 80 ° C, preferably between 60 ° C and 75 ° C.
  • the average temperature in the catalyst zone is preferably 55 ° C to 70 ° C, more preferably 58 ° C to 67 ° C, depending on the pressure in the column.
  • the reactive distillation column is operated at pressures, measured at the top of the column, from 3 to 15, preferably 5 bara to 9 bara, in particular from 7 bara to 8.5 bara.
  • the hydraulic load in the catalytic packing of the column is preferably 10% to 110%, preferably 20% to 70% of its flood point load.
  • Hydraulic loading of a distillation column is understood to be the uniform flow stress of the column cross-section due to the ascending vapor mass flow and the returning liquid mass flow.
  • the upper load limit indicates the maximum load of steam and return fluid, above which the separation effect due to entrainment or jamming of the return fluid by the rising vapor flow decreases.
  • the lower load limit identifies the minimum load, below which the separation effect decreases or collapses due to irregular flow or emptying of the column -. B. the floors. ( Vauck / Müller, "Basic Operations of Chemical Process Engineering", p. 626, VEB Deutscher Verlag für Grundstoffindustrie .)
  • the reactive distillation column is operated with reflux ratios of less than 1.5, in particular with those which are greater than 0.4 and less than 1, preferably between 0.5 and 0.9.
  • the optimum reflux ratio depends on the throughput of the composition of the column feed and the column pressure. However, it always lies in the above ranges.
  • isobutene residual concentrations in the raffinate II common name of 1,3-butadiene and isobutene liberated mixture of C 4 hydrocarbons
  • isobutene residual concentrations in the raffinate II common name of 1,3-butadiene and isobutene liberated mixture of C 4 hydrocarbons
  • the bottoms product of the reactive distillation column preferably consists of MTBE. It preferably contains less than 2500 wppm of methyl sec-butyl ether and less than 2500 wppm of C 8 hydrocarbons.
  • the overhead product of the reactive distillation can in turn be separated into a C 4 -hydrocarbon mixture and methanol, the C 4 -hydrocarbon mixture preferably containing less than 0.5 ppm by weight of MTBE and / or TBA.
  • the pure 1-butene thus prepared contains less than 1000 wppm isobutene and is a sought-after intermediate product. It is used, for example, as a comonomer in the production of polyethylene (LLDPE or HDPE) and of ethylene-propylene copolymers. It is also used as alkylating agent and is the starting material for the production of butan-2-ol, butene oxide, valeraldehyde.
  • a further use of the virtually isobutene-free, raffinate II prepared according to the invention is the preparation of n-butene oligomers, in particular according to the octol process.
  • the hydrocarbons remaining after separation or reaction of the linear butenes from the raffinate II can optionally be worked up after hydrogenation (CSP Complete saturation process) to form isobutane and n-butane.
  • the tert-butyl ether obtained as a bottom product in the reactive distillation can be used for various purposes.
  • cleavage of the tert-butyl ether isobutene of high purity is available.
  • the bottom product of the reactive distillation obtained in the process can be further purified by distillation. In this case, the content of impurities contained in a small amount (for example, methyl sec-butyl ether, C 8 -KW, TBA, alcohols) is reduced.
  • the cleavage of MTBE to obtain isobutene is, for example, in DE 100 20 943 described.
  • the purity of the isobutene obtained depends inter alia on the proportion of methyl sec-butyl ether in the MTBE.
  • a different pre-purified MTBE is used for the cleavage.
  • a bottom product which contains MTBE and the oligomers is precipitated in the reactive distillation column.
  • This mixture can be used as such or after hydrogenation of the olefinic double bonds as Kraftstoftkomponente.
  • this mixture can be fractionated. The individual fractions are then used, as already described.
  • the reactor discharge is transferred to a next reactor for residual butadiene selective hydrogenation 4 , in which hydrogen 5 is fed in turn.
  • the reactor effluent of 4 is transferred to the reactor for butene oligomerization 6 in which mainly the isobutene is converted to dimers, trimers and tetramers.
  • Of the Discharge from this reactor is transferred to a distillation column 7 , in which the butene oligomers are separated off as bottom product 8 .
  • the material stream freed from butene oligomers is passed into a heat exchanger in which the condensable constituents are condensed. Some of these are returned as reflux in the head of the column 7 .
  • non-condensable components are supplied as gaseous exhaust gas stream 17 for further utilization.
  • the distillate of the column 7 is fed together with additional methanol 10 in the MTBE fixed bed stage 9 , with which the remaining isobutene is reacted on the fixed bed catalyst to MTBE.
  • the discharge from the fixed bed stage is fed below the reactive packing 12 into a reactive distillation column 11 .
  • a MTBE 14 -containing stream is assumed, while the top product is moved into a heat exchanger in which the condensable constituents are condensed as isobutene-free n-butene stream. These are partially returned as reflux into the head of the column 11 and discharged as stream 13 from the process.
  • the noncondensable in the heat exchanger portions of the overhead product are fed as gaseous exhaust gas stream 18 for further use.
  • Fig. 2 schematically illustrated method differs from that in Fig. 1 represented method in that instead of Butadienhydrierung 2 butadiene separation 15, for example, an extractive distillation is carried out, which is removed from the isobutene-containing C 4 hydrocarbon stream 1, a large part of the 1,3-butadiene 16 .
  • the butadiene depleted stream from the butadiene separation 15 is then transferred to a reactor for residual butadiene selective hydrogenation 4 , and then as in Fig. 1 further worked up.
  • the following examples are intended to illustrate the invention without restricting the scope of the claims.
  • a HC mixture having the composition shown in Table 2 is hydrogenated over a heterogeneous palladium catalyst in a fixed bed reactor.
  • the hydrogenation analogous to EP 0 523 482 is carried out in two fixed bed reactors, which are operated in series and each equipped with a separator and a liquid circuit. In each of the liquid circuits, a cooler is installed to dissipate the heat of reaction of the hydrogenation can.
  • the hydrogen necessary for the reaction was fed to the reactors according to the amount of 1,3-butadiene to be reacted.
  • the LHSV over the entire plant was 8.5 t / (m 3 h) Percentages of the analyzes are to be read as% by mass.
  • Example 2 -SHP further lowering of the 1,3-butadiene content
  • Residual amounts of 1,3-butadiene, which are still contained in the C 4 -hydrocarbon mixture, can be reduced in a further hydrogenation step.
  • the experiment was carried out with two different raw materials.
  • the feed indicated under 2b corresponds to a composition as obtained from a process according to example 1 (hydrogenation of the 1,3-butadiene contained in crack C 4 ).
  • the feed 2a represents a mixture of C 4 hydrocarbons which is obtained after separation of the 1,3-butadiene from the crack C 4 ( Fig. 2 ).
  • the ion exchanger used by Rohm and Haas had an original acid capacity of 1.7 mol H + / l. To set the desired activity, 40% of the acidic centers were neutralized.
  • the isobutene was oligomerized analogously to Example 3. 51 ml of the partially neutralized ion exchanger were used. The reactor was operated at 22 bara. After a forming phase of 24 hours, the discharge of the reactor was analyzed by gas chromatography. Table 5 summarizes the driving conditions, reactant compositions and analysis, separated by fractions of the C 4 and C 8 fractions.
  • the reactor consisted of a spiral wound tube which was externally tempered by an oil bath.
  • the front part (about the first quarter) of the reactor was not filled with catalyst to preheat the feed to the desired temperature.
  • the back part were in Experiment 5a 125 ml, wrapped in experiment 5b 94 ml ion exchanger.
  • the reactor was heated to (isothermal) 50 ° C via the oil bath.
  • the catalyst used was Amberlyst 15. The pressure of the plant was 8 bara.
  • the C 4 fractions from Example 3 were used as feed. Analyzes and feed rates are given in Table 6. Percentages are read as% by mass. Table 6 - Inlets and analyzes of MTBE fixed bed experiments Experiment 5a Trial 5b Inlet C4 (G / h) 100 100 Feed methanol (G / h) 7.7 6.4 Analysis feed Analysis discharge Analysis feed Analysis discharge methanol (%) 7.15 1.26 6:03 1.11 isobutene (%) 10.87 12:57 9.15 12:57 MTBE (%) 00:00 16:19 00:00 13:50 n-butane (%) 16:19 16:17 14.81 14.82 isobutane (%) 3.84 3.86 3:52 3:51 1-butene (%) 4:48 4:49 40.07 40.10 cis-butene (%) 17.84 17.84 4.10 2.10 trans-butene (%) 39.38 39.39 15.82 15.83 rest (
  • the schematic structure of the reactive distillation column is in FIG. 1 or 2 reflected.
  • the diameter of the column was 312.7 mm.
  • Montz-Pak A3-500 were installed as a reinforcing part.
  • Below, also in the enrichment section of the column were about 11.4 m Katapak SP 12.
  • the lower part of the column consisted of about 3.6 m Montz-Pak A3-500.
  • the inlet position was in the upper third of the lower Montz-Pak A3-500.
  • the feed amount was 700 kg / h. A reflux ratio of 1.09 was set.
  • the distillate was 578.8 kg / h, the bottoms product was 121.2 kg / h. Percentages are read as% by mass.
  • the catalyst used was also Amberlyst 15.
  • the pressure of the plant was 7.5 bara.
  • the feed amount was 700 kg / h.
  • a reflux ratio of 1.09 was set.
  • the distillate was 595.5 kg / h, and the bottoms product was 104.5 kg / h. Percentages are read as% by mass.
  • FIGS. 1 and 2 have the following meanings:

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Claims (7)

  1. Procédé de fabrication couplée d'oligomères de butène et d'éthers de tert.-butyle à partir de courants en C4 contenant de l'isobutène, par
    a) oligomérisation partielle des courants en C4 contenant de l'isobutène sur un catalyseur acide en oligomères de butène, puis
    b) éthérification sous catalyse acide de l'isobutène restant avec un alcool en éthers de tert.-butyle, caractérisé en ce que
    les hydrocarbures polyinsaturés contenus dans les courants en C4 contenant de l'isobutène sont hydrogénés catalytiquement avant l'oligomérisation de l'étape a), en ce qu'un échangeur d'ions, dont les protons ont été partiellement remplacés par des ions métalliques des groupes 1 à 12 du tableau périodique, est utilisé en tant que catalyseur acide à l'étape a), et en ce que l'éthérification sous catalyse acide à l'étape b) est réalisée en au moins deux étapes de réaction, au moins la dernière étape de réaction étant réalisée sous la forme d'une distillation réactive, et en ce que les oligomères de butène obtenus à l'étape a) sont séparés avant l'éthérification sous catalyse acide à l'étape b).
  2. Procédé selon la revendication 1, caractérisé en ce que 1 à 60 % des protons de l'échangeur d'ions utilisé à l'étape a) sont remplacés par des ions métalliques.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'oligomérisation à l'étape a) est réalisée jusqu'à une conversion de l'isobutène de 50 à 95 %.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'oligomérisation à l'étape a) est réalisée en présence d'un modérateur.
  5. Procédé selon la revendication 4, caractérisé en ce que du MTBE, du TBA, du méthanol ou de l'eau est utilisé en tant que modérateur en un rapport en moles de 0,01 à 5 par mole d'isobutène.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que du méthanol ou de l'éthanol est utilisé à l'étape b) en tant qu'alcool.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'hydrogénation des composés polyinsaturés a lieu en au moins deux étapes de réaction, au moins la dernière étape de réaction étant réalisée en présence de 0,05 à 100 ppm en poids de CO.
EP03799530.5A 2003-01-23 2003-12-03 Procede de preparation d'oligomeres butene et de tert-butylethers a partir de flux c4 contenant de l'isobutene Expired - Lifetime EP1585712B1 (fr)

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DE10302457 2003-01-23
DE10302457A DE10302457B3 (de) 2003-01-23 2003-01-23 Verfahren zur Herstellung von Butenoligomeren und tert.-Butylethern aus Isobuten-haltigen C4-Strömen
PCT/EP2003/050930 WO2004065338A1 (fr) 2003-01-23 2003-12-03 Procede de preparation d'oligomeres butene et de tert-butylethers a partir de flux c4 contenant de l'isobutene

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CN112135809A (zh) 2018-05-18 2020-12-25 沙特基础工业全球技术有限公司 利用水合单元生产燃料添加剂的方法
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KR102569585B1 (ko) * 2018-09-18 2023-08-23 사빅 글로벌 테크놀러지스 비.브이. 하나 이상의 연료 첨가제를 효율적으로 제조하기 위한 시스템 및 방법
CN113165996A (zh) 2018-11-20 2021-07-23 沙特基础工业全球技术有限公司 用于生产乙烯以及丁醇和烷基叔丁基醚中的至少一种的方法和系统
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CN1759080A (zh) 2006-04-12
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TW200422288A (en) 2004-11-01
WO2004065338A1 (fr) 2004-08-05
CN1759080B (zh) 2010-05-26
NO20053923L (no) 2005-08-23
EP1585712A1 (fr) 2005-10-19
KR20050098873A (ko) 2005-10-12
PL376455A1 (en) 2005-12-27
US7473812B2 (en) 2009-01-06
ES2523846T3 (es) 2014-12-02
AU2003300251A1 (en) 2004-08-13
PL206183B1 (pl) 2010-07-30
KR101075384B1 (ko) 2011-10-24

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